2-[(trimethylsilyloxy)methyl]pyrolino-1-cyclohexene | 102245-18-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 2-[(trimethylsilyloxy)methyl]pyrolino-1-cyclohexene
• 英文别名: [(2S)-1-(cyclohexen-1-yl)pyrrolidin-2-yl]methoxy-trimethylsilane
• CAS: 102245-18-1
• 化学式: C₁₄H₂₇NOSi
• 分子量: 253.46
• InChiKey: LVFLLKUEWRROTL-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.76
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(trimethylsilyloxy)methyl]pyrolino-1-cyclohexene 、 丙烯腈 在 magnesium chloride 作用下， 以 苯 为溶剂， 生成 (S)-2-β-cyanoethylcyclohexanone
  参考文献：
  名称：

  Asymmetric syntheses of enantiomeric 3-p-fluorophenyl 1,2,4-trioxane analogues of the antimalarial artemisinin

  摘要：

  We have devised an asymmetric synthesis of chiral artemisinin analogues (+)-4a and (-)-4a that retain the tricyclic ring system found in the natural product. The key step in the preparation of (+)-4a involves an asymmetric MgCl2 promoted Michael addition of the (R)-(-)pyrrolidinemethanol-derived enamine 8 to acrylonitrile. This gives the corresponding ketone 9 in 50% yield (>95% ee). Subsequent elaboration of 9 provides the trioxane target (+)-4a in greater than 85% ee. Enantiomeric trioxane (-)-4a was prepared in a similar manner using S-(+)-pyrrolidinemethanol in the first step of the sequence. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01892-4
• 作为产物：
  描述：

  L-脯氨醇 生成 2-[(trimethylsilyloxy)methyl]pyrolino-1-cyclohexene
  参考文献：
  名称：

  Asymmetric syntheses of enantiomeric 3-p-fluorophenyl 1,2,4-trioxane analogues of the antimalarial artemisinin

  摘要：

  We have devised an asymmetric synthesis of chiral artemisinin analogues (+)-4a and (-)-4a that retain the tricyclic ring system found in the natural product. The key step in the preparation of (+)-4a involves an asymmetric MgCl2 promoted Michael addition of the (R)-(-)pyrrolidinemethanol-derived enamine 8 to acrylonitrile. This gives the corresponding ketone 9 in 50% yield (>95% ee). Subsequent elaboration of 9 provides the trioxane target (+)-4a in greater than 85% ee. Enantiomeric trioxane (-)-4a was prepared in a similar manner using S-(+)-pyrrolidinemethanol in the first step of the sequence. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01892-4

文献信息

• Trimethylchlorosilane induced ring opening of 2-alkyloxazolidines to enamine derivatives
  作者：Yoshihiko Ito、Masaya Sawamura、Kazuhiko Kominami、Takeo Saegusa

  DOI：10.1016/s0040-4039(00)95022-6

  日期：1985.1

  2-Alkyloxazolidines (5) were ring-opened by trimethylchlorosilane with N,N-diisopropylamine to give N-[2-(trimethylsilyloxy)alkyll-enamines (6). A MgCl2 promoted Michael reaction of chiral enamines thus prepared was achieved with asymmetric induction.

  通过三甲基氯硅烷与N，N-二异丙基胺使2-烷基恶唑烷（5）开环，得到N- [2-（三甲基甲硅烷氧基）烷基-烯胺（6）。由此制备的MgCl 2促进的手性烯胺的迈克尔反应是不对称诱导的。
• A Simple and Highly Diastereoselective One-Pot Synthesis of Mannich-Bases
  作者：Michael Arend、Nikolaus Risch

  DOI：10.1055/s-1997-946

  日期：1997.8

  A convenient one-pot procedure for the synthesis of β-amino ketones 5 from economical shelf reagents is described. Iminium salts 3 are generated in virtually quantitative yields from secondary amines 1 and aldehydes 2 mediated by NaI/Me3SiCl/NEt3. Subsequently, the salts 3 are used for the in situ aminoalkylation of enamines 4. The method provides the Mannich bases 5 in high yields and excellent diastereoselectivities (>96 % ds). It can also be applied for the aminoalkylation of other nucleophiles such as imines or electron-rich aromatic compounds.

  描述了一种方便的一锅法合成β-氨基酮5的方法，使用经济的现成试剂。从二级胺1和醛2在NaI/Me3SiCl/NEt3的介导下几乎定量地产生亚胺盐3。随后，这些盐3用于在位氨基烷基化烯胺4。该方法以高产率和优良的立体选择性（>96% ds）提供Mannich碱5。它还可以应用于其他亲核试剂的氨基烷基化，如亚胺或富电子芳香化合物。
• FIORAVANTI, STEFANIA;LORETO, M. ANTONIETTA;PELLACANI, LUCIO;TARDELLA, PAO+, J. CHEM. RES. SYNOP.,(1987) N 9, 310-311
  作者：FIORAVANTI, STEFANIA、LORETO, M. ANTONIETTA、PELLACANI, LUCIO、TARDELLA, PAO+

  DOI：——

  日期：——
• Asymmetric syntheses of enantiomeric 3-p-fluorophenyl 1,2,4-trioxane analogues of the antimalarial artemisinin
  作者：Paul M. O'Neill、Alison Miller、Jamie F. Bickley、Feodor Scheinmann、Chang Ho Oh、Gary H. Posner

  DOI：10.1016/s0040-4039(99)01892-4

  日期：1999.12

  We have devised an asymmetric synthesis of chiral artemisinin analogues (+)-4a and (-)-4a that retain the tricyclic ring system found in the natural product. The key step in the preparation of (+)-4a involves an asymmetric MgCl2 promoted Michael addition of the (R)-(-)pyrrolidinemethanol-derived enamine 8 to acrylonitrile. This gives the corresponding ketone 9 in 50% yield (>95% ee). Subsequent elaboration of 9 provides the trioxane target (+)-4a in greater than 85% ee. Enantiomeric trioxane (-)-4a was prepared in a similar manner using S-(+)-pyrrolidinemethanol in the first step of the sequence. (C) 1999 Elsevier Science Ltd. All rights reserved.